The electrophysical property of saturated rocks is very important for reservoir identification and evaluation. In this paper, the lattice Boltzmann method (LBM) was used to study the electrophysical property of rock saturated with fluid because of its advantages over conventional numerical approaches in handling complex pore geometry and boundary conditions. The digital core model was constructed through the accumulation of matrix grains based on their radius distribution obtained by the measurements of core samples. The flow of electrical current through the core model saturated with oil and water was simulated on the mesoscopic scale to reveal the non-Archie relationship between resistivity index and water saturation (Ⅰ-Sw). The results from LBM simulation and laboratory measurements demonstrated that the Ⅰ-Sw relation in the range of low water saturation was generally not a straight line in the log-log coordinates as described by the Archie equation. We thus developed a new equation based on numerical simulation and physical experiments. This new equation was used to fit the data from laboratory core measurements and previously published data. Determination of fluid saturation and reservoir evaluation could be significantly improved by using the new equation.